Method of manufacturing permanently fusible and soluble synthetic resins from non-fusible phenolaldehyderesins.



an s'ra'rns "rn rnur orri g.

' nunwre seamen, or mousse-so, (31mm.

METHOD GEMANUFACTUBING 'PERMANENTLY FUSIBLE AND SOLUBLE SYNTHETIC I BESINS FROM. NOII -FUSIBLE PHENOLALDEHYDERESINS.

5 7 V Specification of ma num. t t 12, vat Drawing. Application filedJune 28,1915. Serial a... 86,884.

To all whom it may concern: pressure with and without the admixture ofBe it known that I, 'Dr. LUDWIG BEREND, acids or acid salts as contactmeans. This citizen of Germany, subject of the King of fact is the moresurprising because it was Prussia and Emperor of Germany, resi ing notto be expected that the same resins which 5 at Landg'rabenweg "14,Amoneburg-onsthemay be added to the condensation products 60 Rhine, inthe Grand Duchy of Hesseand before they are converted into non-fusibleEmpire of Germany, have invented new and substances by heating them to'tempera-' useful Improvements in Methods of Manu-' tures which mostlyremain below 130, are facturing Permanently Fusible and Soluble able toagain-render these non-fusible resins 10 Synthetic Resins fromNon-Fusible Phenol-' fusible at higher temperatures. A.lso the 6 5 aldehderesins, of which the following is a accelerating eifect of theadmixture of, acids speci cation. and acld salts on the conversion ofthe non- The synthetic resins which are obtained fusible substances intofusible substances by the reaction of formaldehyde on phenols verysurprismg, for the reason that in sev-" "15. may be divided into-threeprincipal classes eralspecifications it is recommended to add 79 Thefirst class comprises the non-fusible and acids and acid salts forincreasing the speed insoluble resins, which when heated to of hardeningthe phenolaldehyde resins. higher temperatures will decomposeand car-(German Patent 214,194). The rendering .bonize.. To the second classbelong. the soluble of thenou-fusible resins may also barelyfusiblecondensation products, which, be eflfected in the presence orwlth admix- 5 when heated, very quickly become non-fus1-. ture of bases,basic or neutral salts.

" ble and insoluble. To the third class are In accordance withthese justnamed obrec'koned the resins which even when heated servations' I havefurther found that it is for a prolonged period either remainperpossible to prevent by the addition of natumanently fusible andsoluble, or only very ral or artificial resins the very rapidlyprogradually become more or less non-fusible ceeding conversion of thecondensation prodand insoluble, ucts of the second group intonon-fusible Of these three classes of resins those of products. So forexample, it will be posthe first class have hitherto obtained the sibleto not only render again soluble by the 30 greatest importance, inparticular in elecaid of natural or artificial resins'thecomtricalengineering. Two methods are 'empletely non-fusible andinsoluble resins, ployed for manufacturing articles from which areobtained from 0-, mand p-crethese latter resins. They are eithermanusoldialcohols by heating, but also to comfactured from the prelminary stages which pletely avoid by an addition of these natu- 35 arestillfusible or,-at higher temperatures ral or-artificial resins theconversion of the Y and'pressures, still plastic, by heating thesecresolalcohol-resins by heating into non- -in molds at the atmosphericor at "an infusible products. Furthermore it is now creased pressure, orfrom completely haralso ossible to produce permanently soluble denedresin blocks by mechanically working and sible resin compounds-of anydesired 40 these. For increasing the elasticity, for re-- degree ofhardness by heatingsuitable'mixv ducingthe rice and for other purposesfilltures of natural or synthetic resins with such ing materia s ofvarious kinds are embodied fusible, soluble phenolaldehyde resins of thein the condensation substances from phethird class, which'by prolongedheatingbe 11015 and formaldehydes to be hardened, become more and morehard and eventually 45 fore they are converted into non-fusible more orless non-fusible, and will therefore products. Among others, also resinsare readily burn to the vesel and be carbonized, emlployed as suchfillingmaterials. without there being any danger of these now haveobserved the surprising and resin compounds being decomposed in thepeculiar fact that it is possible to convert new process. Y 60 suchnon-fusible resins again into fusible The great importance of thehereinbefore and soluble resins by heating them with disclosed inventionis, briefly stated, as folnatural or synthetic resins of various kinds,lows:

also with the aforementioned resins em- Firstly the new method affordsthe possiployed as filling materials, to higher tembility of againconverting the'large quan-l 55 peratures at re need, ordinary ormcreased titles of non-fusible resins, forming the.

' cent.

scrap from the mechanical working of non-fusible resins, or obtained asdefective or worn articles, in a most simple and economic manner intosoluble and fusible sub stances.

A special advantage of the new method consists in its allowing ofremoving from articles which, to a certain degree will withstand heat,coatings consisting of non-fusible resins and which have becomedefective and unserv-iceable, so that not only these nonfusible resinmaterials but also the articles coated therewith may be utilized anew.So, for example, metallic wires coated for the purpose of insulationwith non-fusible resins may be treated in this manner. q

Furthermore the new method, also allows of always converting partly orcompletely non-fusible resin, which has unintendedly been formed in thecondensation process, into utilizable fusible resin.

Neither phenols nor mixtures of phenols can be condensed withformaldehyde alone, with or without contact means, in quantitativeproportion to completelyv fusible and soluble resins. Accordin to thecharacter of the phenol or the mixture of phenols, respectively, and themanner of performing the condensation process it was in this case tillnow necessary to work with amore or less great surplus of phenol inorder to avoid the formation of partly non-fusible products.

With crude cresols, containing about 40% m-cresol, only of the cresolemployed may be converted by condensation without addition of contactmeans, into fusible resin. If, however, before or during the condensation sufl'cient quantities of a fusible artificial or natural resinare added to the reaction masses, it will be possible to convert in oneoperation all the phenol into fusible resin. If, nevertheless, aconversion into non-fusible resin should occur, it will only benecessary to highly heat the material further with very small quantitiesof natural or fusible artificial resins, in order to obtain the desiredfusible resi- Examples.

(1.) Heat for one hour and a half 50 grams of finely powderednon-fusible cresol resin, obtained by heating 150' grams of fusiblecresol resin with 4.5 grams of trioxymethylene, with 50 grams of hotcolophany at a temperature of 260-270. degrees The non-fusible resinwill dissolve under violent foaming. The resin obtained is soluble, forexample, in a cold mixture of alcohol and benzol and may be boiled withlinseed oil to a clear varnish.

(2.) Heat 100 grams of coarsely powin the colophony,

dered non-fusible resin, which is obtained from crude m-cresol by theaid of hydrochloric acid as contact means, with 150 grams of colophonyfor 3 hours under pressure at a temperature of 240 C. The extremely hardresin will then completely dissolve in boiling linseed oil.

3 Heat 75 grams of the artificial infusible resin used in Example 2 for3 hours under pressure with 125 grams of cumarone resin at 240 C. Theresin will then be completely soluble in a mixture of benzol andalcohol.

(4.) Heat 7 5 grams of the infusible resin used in Examples 2 and 3 inan autoclave (digesting-furnace) for 7 hours with 100 grams of palmresin (gutta resin) to 250 Whereas after two hours of heating onlypartial solution will have resulted, the final product will dissolveclear in a mixture of benzol. and alcohol.

(5.) Heat 100 parts of non-fusible resin, which is obtained bycondensation of crude cresol without addition of a contact means, with150 parts of colophony and 10 parts of chlorid of ammonia for 3 hours ina closed vessel at a temperature of 250 C. The resin compound obtainedwill then completely dissolve in a mixture of-benzol and alcohol. Thechlorid of ammonia remains undissolved.

(6.) Heat equal parts of p-cresol-di-alco 1101 and colophony underordinary pressure at 280 C.; whereas p-cresol-di-alcohol when heated foritself, will very quickly become non-fusible, splitting ofl"formaldehyde and water, this alcohol Will'dissolve very quickly forminga clear resin compound therewith.

Having now described my invention what I claim and desire to secure byLetters Patent of the United States is:

1. A process for the manufacture of fusible and soluble artificialresins from unmeltable, insoluble phenol-aldehyde resins consisting inheating these non-fusible resms with tact media.

2. A process for the manufacture of fusible and soluble artificialresins from unmeltable, insoluble phenol-aldehyde resins consisting inheating these non-fusible resins with other resins in "the presence ofacid contact media.

other resins in the presence of con- In testimony whereof I havehereunto set my hand in presence of two subscribing witnesses.

LUDWIG BEREND.

